Treated Biodiesel Glycerin

ABSTRACT

Disclosed are compositions that include treated biodiesel glycerin. The disclosed compositions may be utilized as soil-amendments for controlling pests, weeds and for enhancing growth of plants. The biodiesel glycerin utilized in the disclosed compositions may be treated by one or more steps including neutralization, heating, refluxing, condensing, and distilling.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority under 35 U.S.C. §119(e)to prior U.S. provisional application No. 60/904,672, filed on Mar. 2,2007; application No. 60/937,128, filed on Jun. 26, 2007; applicationNo. 60/937,243, filed on Jun. 26, 2007; and application No. 60/964,913,filed on Aug. 15, 2007; the contents of which are incorporated byreference herein in their entireties.

BACKGROUND

The field of the invention relates to glycerin by-products of biodieselfuel production. In particular, the field of the invention related tothe use of treated glycerin by-products of biodiesel fuel production assoil-amendments.

Biodiesel fuels (BDF) are important sustainable energy sources. They areavailable commercially for use as alternatives for replacement of fuelsderived from coal, petroleum, and other fast dwindling and non-renewablefossil energy sources. BDF usually are esters of fatty acids with simplealcohols, principally methanol. The production of fatty acids for BDFmanufacture may be based on a transesterification reaction of sodiummethylate with animal or vegetable fats, which are esters of acids withglycerin (1,2,3-propanetriol). This is followed by separation ofglycerin and other impurities from the methylated fatty acids, usuallybased on the fact that glycerin has a higher density than methylatedfatty acids and sinks to the bottom of a batch reaction mixture. The BDFprocess thus results in accumulation of significant quantities of crudeglycerin as by-product (i.e., “BDF glycerin”).

BDF glycerin commonly contains about 65-85% glycerin and otherimpurities that include acrolein, monoglycerides, and “high boilingcompounds.” Production of commercial-grade glycerin, which is usuallyabout 90-95% glycerin, requires removal of these impurities forpotential markets. The increased cost of purification and the surfeit ofglycerin in the world market today translate into a serious disposalproblem for this by-product of BDF manufacture. Most crude glycerintoday often is sold for burning as a source of energy. The oversupply ofglycerin is considered one of the major problems in development of thebiodiesel industry and new compositions and uses for BDF glycerin aredesirable.

SUMMARY

Disclosed are compositions that comprise treated crude glycerin that isobtained as a by-product of methods for producing biodiesel fuel. Thedisclosed compositions may be useful as soil-amendments for controllingpests, controlling weeds, or enhancing growth of crops as a fertilizer.The disclosed composition may be utilized as soil-amendments eitheralone or in combination with additional ingredients.

In some embodiments, the disclosed compositions are utilized assoil-amendment compositions for controlling soil-bourne pests, weeds, orboth, and comprise: (a) an effective amount of a treated crude glycerincomposition, where the crude glycerin composition is obtained as aby-product of a reaction mixture for producing biodiesel fuel and thecrude glycerin composition is treated by: (i) adjusting the pH of thecrude glycerin composition to about 4.0-6.8 (preferably 5.5-6.8, andmore preferably 5.8-6.5) to obtain a neutralized composition; and (ii)removing an insoluble precipitate from the neutralized composition;thereby obtaining the treated crude glycerin composition; and optionally(b) an effective amount of an nitrogen source (e.g., an organic orinorganic nitrogen source); where the composition has a molar ratio oftotal carbon to total nitrogen (C:N) of about (22.4-5.6):1, andpreferably about (16.8-11.2):1. In further embodiments, the crudeglycerin composition is further treated by: (iii) performing one or moresteps that include heating, refluxing, condensing, or distilling theneutralized composition; and optionally (iv) removing or collecting avolatile distillate fraction; thereby obtaining the treated crudeglycerin composition.

The disclosed compositions may be utilized as soil-amendmentcompositions for controlling soil-bourne pests, weeds, or both. In someembodiments, the soil-bourne pests are parasitic nematodes such asRotylenchulus reniformis. In some embodiments, the disclosedcompositions may be effective for reducing parasitic nematodespopulations in amended soil by at least about 50% (preferably by atleast 60%, 70%, 80%, or 90%) when applied at an application rate ofabout 1 ml/kg soil (or optionally at a higher rate of about 2 ml/kgsoil, 3 ml/kg soil, or 4 ml/kg soil). In further embodiments, thedisclosed compositions may not have a significantly detrimental effecton beneficial nematodes. For example, in some embodiments the disclosedcompositions do not reduce beneficial microbivorous nematodes in amendedsoil by more than about 50% (preferably by no more than least 40%, 30%,20%, or 10%) when applied at an application rate of about 1 ml/kg soil(or optionally at a higher rate of about 2 ml/kg soil, 3 ml/kg soil, or4 ml/kg soil).

The crude glycerin utilized to prepare the disclosed compositions may beobtained as a by-product of a reaction mixture for producing biodieselfuel (e.g., a reaction mixture for producing alkyl esters of fatty acidsvia transesterification). The reaction mixture for producing biodieselfuel may include: (a) animal fat, vegetable oil, or a mixture thereof;(b) a base, wherein the reaction mixture has a pH of at least about 11;and (c) an alcohol. Suitable bases may include, but are not limited to,metal hydroxides (e.g., NaOH and KOH), metal alkoxides (e.g., NaOCH₃ andKOCH₃), and mixtures thereof. In some embodiments, the base is apotassium salt (e.g., KOH, KOCH₃, or mixture thereof). Suitable alcoholsmay include, but are not limited to, aliphatic alcohols such asmethanol, ethanol, or a mixture thereof.

The crude glycerin utilized to prepare the disclosed compositionsincludes glycerin (e.g., at a concentration of about 65-85%) and mayinclude additional components, which may include, but are not limitedto, enal compounds (e.g., acrolein or “2-propenal”), residual glycerides(e.g., monoglycerides), and residual volatiles (e.g., alcohol such asmethanol or ethanol). The crude glycerin typically is treated prior tobeing utilized to prepare the disclosed composition. Prior to beingtreated, the crude glycerin may have a basic pH (e.g., greater than atleast about 11 or 12). After being treated, the crude glycerin may havea lower pH (e.g., about 4.0-6.8, preferably about 5.5-6.8, and morepreferably about 5.8-6.5). The treated crude glycerin includes glycerin(e.g., at a concentration of about 65-85%) and may include additionalcomponents, which may include, but are not limited to, enal compounds orenriched amounts of enal compounds (e.g., acrolein or “2-propenal”),reduced amounts of residual glycerides (e.g., monoglycerides), andreduced amounts of residual volatiles (e.g., alcohol such as methanol orethanol).

In some embodiments, the pH of the crude glycerin is adjusted by addingan acid to the crude glycerin. Suitable acids include, but are notlimited to, organic acids such as carboxylic acids (e.g., acetic acid,propionic acid, butyric acid, valeric acid, or mixtures thereof),inorganic acids (e.g., phosphoric acid, sulfuric acid, or mixturesthereof), or mixtures of organic acids and inorganic acids. Suitableacids may include polyhydroxycarboxylic acids (e.g., citric acid). Insome embodiments, the acid is a mixture an organic acid and an inorganicacid, such as a mixture of propionic acid and phosphoric acid(preferably at a ratio of about (3-1):1 or at a ratio of about 2:1).

The disclosed compositions may be prepared from crude glycerin thatincludes, as an additional component, an enal compound such as acrolein(i.e., 2-propenal). The crude glycerin may be treated in order toincrease the amount of enal compounds present in the crude glycerin. Forexample, in some embodiments, the crude glycerin may be treated byheating the crude glycerin to about 200-300° C. In other embodiments,the crude glycerin may be treated by reacting the crude glycerin withsodium bisulfate or potassium bisulfate. In some embodiments, thedisclosed compositions may include at least about 1% acrolein(preferably at least about 2%, 3%, 4%, or 5% acrolein).

In some embodiments, the crude glycerin optionally is treated byperforming one or more steps such as heating, refluxing, condensing, anddistilling. For example, the pH of the crude glycerin may be adjusted toabout 4.0-6.8 (preferably about 5.5-6.8, and more preferably about5.8-6.5) to obtain a neutralized composition; optionally, any solidprecipitate formed in the neutralized composition may be removed; andoptionally, the neutralized composition may be heated to a temperaturegreater than about 80° C. (preferably greater than about 85° C. orgreater than about 90° C.) under vacuum. A volatile distillate fractionmay be removed from the composition thusly heated leaving a retainedfraction. In further embodiments, the retained fraction, may be heated,refluxed, condensed, or distilled, for example, by heating the retainedfraction to a temperature of about 200-300° C. (preferably about220-250° C.) for at least about 30 minutes (preferably for about 60-90minutes), thereby obtaining a refluxed glycerin composition. Therefluxed glycerin composition optionally may be heated to temperaturesranging from about 40-250° C. and one or more distillates may becollected. In some embodiments, a distillate is collected where thedistillate has a boiling point range of about 50-100° C. The refluxedglycerin and collected distillates may have an enriched concentration ofenal compounds (e.g., at least about 1%, 2%, 3%, 4%, 5%, 10%, or 15%acrolein).

The disclosed composition may be utilized as soil-amendments. In someembodiments, the composition includes a treated crude glycerincomposition and further may include a nitrogen source. In someembodiments, the disclosed compositions include a treated crude glycerincomposition and nitrogen source and have a molar ratio of total carbonto total nitrogen (C:N) of about (22.4-5.6):1, and preferably about(16.8-11.2):1. Nitrogen sources may include organic nitrogen sources,inorganic nitrogen sources, or a mixture thereof. Suitable organicnitrogen sources may include, but are not limited to, urea, casein, andmixtures thereof. Addition suitable sources of organic nitrogen mayinclude, but are not limited to, manure (e.g., dairy manure, cage manureincluding egg layers' manure, or mixtures thereof), hay (e.g., legumehay, grass hay, or mixtures thereof), and meal (e.g., alfalfa meal,soybean meal, blood meal, cottonseed meal, crab meal, fish meal, feathermeal, or mixtures thereof). Suitable inorganic nitrogen sources mayinclude, but are not limited to, ammonium salts (e.g., ammoniumsulfate), nitrite salts, nitrate salts (e.g., potassium nitrate orammonium nitrate), and mixtures thereof. Preferably, the nitrogen sourcemay be readily assimilated by plants when the disclosed compositions areutilized as soil-amendments. The nitrogen source may be added to thetreated glycerin composition as a solid or as a solution. In furtherembodiments, the disclosed compositions do not include a nitrogen sourceand may be added to soil as an amendment in order to achieve in theamended soil a molar ratio of total carbon to total nitrogen (C:N) ofabout (22.4-5.6):1, and preferably about (16.8-11.2):1, where the soil,prior to amendment, includes a nitrogen source.

The disclosed compositions typically include a treated crude glycerincomposition and further may include additional components that aresuitable as soil-amendments. For example the disclosed compositions mayinclude additional components such as pesticides (e.g., nematocides,insecticides, fungicides, and herbicides), fertilizers, or both. In someembodiments, the disclosed compositions include a treated crude glycerincomposition and further include a sulfur compound.

Also disclosed are methods for preparing the disclosed compositions. Insome embodiments, the disclosed methods include methods for preparing asoil-amendment composition for controlling soil-bourne pests, weeds, orboth, and may include the steps of (i) adjusting the pH of a crudeglycerin composition to about 4.0-6.8 (preferably 5.5-6.8, and morepreferably 5.8-6.5) to obtain a neutralized composition, where the crudeglycerin composition is obtained as a by-product of a reaction mixturefor producing biodiesel fuel; and (ii) removing an insoluble precipitatefrom the neutralized composition; thereby obtaining the treated crudeglycerin composition. The treated crude glycerin composition may beutilized as a soil-amendment composition or optionally further may betreated (e.g., subjected to heating, refluxing, condensation, ordistillation) or further may be combined with additional ingredients(e.g., a nitrogen source). In some embodiments, the crude glycerincomposition is further treated by: (iii) performing one or more stepssuch as heating, refluxing, condensing, and distilling the neutralizedcomposition; and optionally (iv) removing or collecting a volatiledistillate fraction; thereby obtaining the treated crude glycerincomposition suitable for use as a soil-amendment composition. In furtherembodiments, the treated crude glycerin composition further is combinedwith an effective amount of nitrogen source; wherein the composition hasa molar ratio of total carbon to total nitrogen (C:N) of about(22.4-5.6):1, and preferably of about (16.8-11.2):1.

Also disclosed are methods for controlling soil-bourne pests, weeds, orboth. The methods may include applying the disclosed compositions as aliquid soil-amendment composition at an application rate of at leastabout 1 ml/kg soil (optionally at an application rate of at least about2 ml/kg soil, 3 ml/kg soil, or 4 ml/kg soil). The selected applicationrates may achieve an effective concentration of acrolein in soil forcontrolling pest, weeds, or both (e.g., at least about 25 mg acrolein/kgsoil, 50 mg acrolein/kg soil, 100 mg acrolein/kg soil, 200 mgacrolein/kg soil, or 300 mg acrolein/kg soil). The soil-amendmentcomposition may comprise an effective amount of a treated crude glycerincomposition, where the crude glycerin composition is obtained as aby-product of a reaction mixture for producing biodiesel fuel and thecrude glycerin composition is treated by: (i) adjusting the pH of thecrude glycerin composition to about 4.0-6.8 (preferably 5.5-6.8, andmore preferably 5.8-6.5) to obtain a neutralized composition; and (ii)removing an insoluble precipitate from the neutralized composition;thereby obtaining the treated crude glycerin composition. Optionally,the crude glycerin composition may be further treated by (iii)performing one or more steps such as heating, refluxing, condensing, anddistilling the neutralized composition; and optionally (iv) removing orcollecting a volatile distillate fraction; thereby obtaining the treatedcrude glycerin composition. Optionally, the soil-amendment furthercomprises an effective amount of an organic nitrogen source; where thesoil-amendment composition has a molar ratio of total carbon to totalnitrogen (C:N) of about (22.4-5.6):1, and preferably of about(16.8-11.2):1.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1. The effect of a neutralized bioglycerin composition (seeExample 1) at various application rates (0 ml/kg soil, 1 ml/kg soil, 2ml/kg soil, 3 ml/kg soil, 4 ml/kg soil, or 5 ml/kg soil) with or withoutadded urea (150 mg/kg soil) on nematode population (Rotylenchulusreniformis/100 ml soil) was assessed.

FIG. 2. The effect of a neutralized bioglycerin composition (seeExample 1) at various application rates (0 ml/kg soil, 1 ml/kg soil, 2ml/kg soil, 3 ml/kg soil, 4 ml/kg soil, or 5 ml/kg soil) with or withouturea (150 mg/kg soil) on nematode population (Microbivorous/100 ml soil)was assessed.

FIG. 3. The effect of a neutralized bioglycerin composition (seeExample 1) at various application rates (0 ml/kg soil, 1 ml/kg soil, 2ml/kg soil, 3 ml/kg soil, 4 ml/kg soil, or 5 ml/kg soil) with or withouturea (150 mg/kg soil) on nematode population (Dorylaimida/100 ml soil)was assessed.

FIG. 4. The effect of distilled fractions of neutralized bioglycerincompositions (see Examples 1-3, fractions collected at 130-245° C.,245-250° C., 250° C., 250-255° C., 255-260° C., and 260-275° C.) atvarious application rates (0 ml/kg soil, 1 ml/kg soil, or 3 ml/kg soil)on nematode population (Rotylenchulus reniformis/100 ml soil) wasassessed.

FIG. 5. The effect of distilled fractions of neutralized bioglycerincompositions (see Examples 1-3, fractions collected at 130-245° C.,245-250° C., 250° C., 250-255° C., 255-260° C., and 260-275° C.) atvarious application rates (0 ml/kg soil, 1 ml/kg soil, or 3 ml/kg soil)on nematode population (Microbivorous/100 ml soil) was assessed.

FIG. 6. The effect of distilled fractions of neutralized bioglycerincompositions (see Examples 1-3, fractions collected at 130-245° C.,245-250° C., 250° C., 250-255° C., 255-260° C., and 260-275° C.) atvarious application rates (0 ml/kg soil, 1 ml/kg soil, or 3 ml/kg soil)on nematode population (Dorylaimida/100 ml soil) was assessed.

FIG. 7. The effect of distilled fractions of neutralized bioglycerincompositions (see Examples 1-3, fractions collected at 73° C., 73-76°C., 76-86° C., 86-96° C., 96-130° C., and 245-250° C.) at variousapplication rates (0 ml/kg soil, 1 ml/kg soil, or 3 ml/kg soil) onnematode population (Rotylenchulus reniformis/100 ml soil) was assessed.

FIG. 8. The effect of distilled fractions of neutralized bioglycerincompositions (see Examples 1-3, fractions collected at 73° C., 73-76°C., 76-86° C., 86-96° C., 96-130° C., and 245-250° C.) at variousapplication rates (0 ml/kg soil, 1 ml/kg soil, or 3 ml/kg soil) onnematode population (Microbivorous/100 ml soil) was assessed.

FIG. 9. The effect of distilled fractions of neutralized bioglycerincompositions (see Examples 1-3, fractions collected at 73° C., 73-76°C., 76-86° C., 86-96° C., 96-130° C., and 245-250° C.) at variousapplication rates (0 ml/kg soil, 1 ml/kg soil, or 3 ml/kg soil) onnematode population (Dorylaimida/100 ml soil) was assessed.

FIG. 10. The effect of a neutralized bioglycerin composition (seeExample 1) at various application rates (0 ml/kg soil, 1 ml/kg soil, 2ml/kg soil, 3 ml/kg soil, 4 ml/kg soil, or 5 ml/kg soil) with or withoutadded urea (150 mg/kg soil) on nematode population (Rotylenchulusreniformis/100 ml soil) was assessed.

FIG. 11. The effect of a neutralized bioglycerin composition (seeExample 1) at various application rates (0 ml/kg soil, 1 ml/kg soil, 2ml/kg soil, 3 ml/kg soil, 4 ml/kg soil, or 5 ml/kg soil) with or withoutadded urea (150 mg/kg soil) on cotton plant emergence (cotton plant perpot) was assessed. The presence of urea was observed to result in anincrease in the number of cotton plants per pot.

FIG. 12. The effect of a neutralized bioglycerin composition (seeExample 1) at various application rates (0 ml/kg soil, 1 ml/kg soil, 2ml/kg soil, 3 ml/kg soil, 4 ml/kg soil, or 5 ml/kg soil) with or withoutadded urea (150 mg/kg soil) on cotton plant shoot weight (grams) wasassessed. The presence of urea was observed to result in an increase inthe weight of fresh shoots.

DETAILED DESCRIPTION

The present invention is described herein using several definitions, asset forth below and throughout the application.

Unless otherwise specified, the terms “a” or “an” mean “one or more.”

As used herein, “about” and “substantially” will be understood bypersons of ordinary skill in the art and will vary to some extent on thecontext in which they are used. If there are uses of the term which arenot clear to persons of ordinary skill in the art given the context inwhich it is used, “about” will mean up to plus or minus 10% of theparticular term and “substantially” will mean more than plus or minus10% of the particular term.

As used herein, “crude glycerin,” “biodiesel glycerin,” “biodiesel fuelglycerin,” “BDF glycerin,” or “bioglycerin” refer to a glycerincomposition that is obtained as a by-product of a reaction for producingbiodiesel fuel (BDF), and which may be further treated or leftuntreated. The reaction for producing BDF may include atransesterification reaction or alcoholysis reaction that occurs in abasic reaction mixture (e.g., having a pH greater than about 11)comprising triglycerides (e.g., which are present in animal or vegetablefats or oils) and alcohol (e.g., methanol or ethanol). The reactionmixture may produce fatty acid alkyl esters (e.g., fatty acid methylesters) and glycerin. As used herein, “glycerin,” “glycerine,” or“glycerol” refers to the compound 1,2,3, propanetriol.

The disclosed compositions may include liquid compositions. Unlessindicated as otherwise, percentage concentrations refer to percentage ona volume/volume basis.

The disclosed compounds may be utilized as soil-amendments. Glycerin isnot only a good carbon source for some microorganisms in soil but BDFsglycerin also contain acrolein, potentially a desirable component indevelopment of glycerin-based organic amendments. The heating ofglycerin at to high temperatures results in dehydration, re-arrangementand formation of enal compounds such as acrolein (i.e., “2-propenal”)(Merck Index. 1989. 11^(th) Edition. Merck & Co., Inc. Rahwayt, J. J.U.S.A.; and Whitmore, F. C. 1951. Organic Chemistry. Vol. 1. DoverPublications, Inc. New York; incorporated by reference herein in theirentireties). Acrolein is a toxic compound registered for use in controlof aquatic weeds (Meister Pro. 2006. Crop Protection Handbook. MoisterMedia, Willoughby, Ohio, incorporated by reference herein in itsentirety). Research at Auburn University has demonstrated that acroleinhas fungicidal and nematocidal activities in greenhouse and fieldexperiments (Belcher, J. L., R. H. Walker, R. Rodriguez-Kabana, E.Guertal, and L. E. Simmons, 2005, Proceedings Annual InternationalResearch Conference on Methyl Bromide Alternatives and EmissionsReductions, Oct. 31-Nov. 3, 2004, San Diego, Calif., Paper No. 24;Belcher, J. L., R. H. Walker, and K Rodriguez-Kabana, 2004, ProceedingsAnnual International Research Conference on Methyl Bromide Alternativesand Emissions Reductions, Oct. 31-Nov. 3, 2004, Orlando, Fla., Paper No.23; Rodriguez-Kabana et al., U.S. patent application Ser. No.11/260,771, filed Oct. 27, 2005; Rodriguez-Kabana, R, L. J. Simmons, R.H. Walker, E. A. Guertal, & D. H. Teem, 2004, Proceedings AnnualInternational Research Conference on Methyl Bromide Alternatives andEmissions Reductions, Oct. 31-Nov. 3, 2004, Orlando, Fla. Paper No. 22;Rodriguez-Kabana, R., E. A. Guertal, R. H. Walker, and D. H. Teem, 2003,Proceedings Annual International Research Conference on Methyl BromideAlternatives and Emissions Reductions, Nov. 3-6, 2003, San Diego,Calif., Pages 51-1 to 51-7; incorporated herein by reference in theirentireties).

The disclosed compositions may include enal compounds. Enal compoundsmay include dehydration products of glycerol compounds. As used herein,enal compounds include 2-propenal (i.e., acrolein) and polymers thereof.In some embodiments, the disclosed compositions may include at leastabout 1%, 2%, 3%, 4%, 5%, 10%, or 15% 2-propenal and polymers thereof.

The disclosed compositions may include treated glycerin compositions andmay be used as soil-amendments that exhibit fertilizing activity. Forexample, the disclosed compositions may include one or more ofassimilable potassium, phosphorus, and nitrogen. In some embodiments,the treated glycerin composition is prepared from a crude glycerincomposition that is obtained from a transesterification reaction inwhich a potassium salt is used as a catalyst or a basifying agent (e.g.,KOH or KOCH₃). In further embodiments, the crude glycerin composition istreated with a phosphorus-containing acid (e.g., phosphoric acid orphosphorous acid). In even further embodiments, a nitrogen source may beadded to the treated glycerin composition to provide a soil-amendmentcomposition having a suitable C:N ratio.

Incorporation into soil of organic matter with the appropriate C:N ratiois one of the best methods to suppress plant parasitic nematodes andother soil-borne pests. Stimulation of microbial activities in soilfollowing incorporation of organic amendments has been repeatedlydemonstrated to results in control of plant parasitic nematodes, anumber of phytopathogenic fungi and even some insects and weeds.(Rodriguez-Kabana, R, and M. H. Pope, Nematropica 11: 175-186 (1986);Rodriguez-Kabana, R., G. Morgan-Jones, and T. Chet. 1987. Plant and Soil100: 237-247; Stirling, G. K 1991. Biological control of plant parasiticnematodes: progress, problem and prospects. Wallingford, Oxon, UK, CABInternational, pp. 282; incorporated herein by reference in theirentireties). Considerable research has been directed to the preparationof organic amendments based on agricultural wastes and other by-productsof human activities, e.g., chicken and other manures, sewage and otherurban ordures, in order to dispose of these materials in anenvironmentally acceptable manner (Stirling, 1991). In some embodiments,the disclosed compositions include a nitrogen source which may be anorganic nitrogen source or an inorganic nitrogen source. Preferably, thenitrogen source is soluble in glycerin. The disclosed compositions mayhave a suitable C:N ratio (e.g., a C:N ration that about (22.4-5.6):1 orabout (16.8-11.2):1).

As used herein, the phrase “effective amount” or “effective rate” shallmean that amount or rate that provides the specific response for whichthe composition is applied in a significant number of applications. Thedisclosed compositions may include an effective amount of the treatedglycerin compositions to achieve a pesticidal effect (e.g., anematocidal, a fungicidal, an herbicidal, or insecticidal effect) whenapplied at a given application rate. In some embodiments, the treatedglycerin compositions may include enal compounds (e.g., 2-propenal).Effective amounts of enal compounds (e.g., 2-propenal) and effectiveapplication rates for compositions that comprise enal compounds forcontrolling pests and weeds are disclosed in U.S. patent applicationSer. No. 11/260,771, which is incorporated herein by reference in itsentirety. In some embodiments, the disclosed compositions include2-propenal and are applied to soil as an amendment at an applicationrate that achieves an effective concentration of 2-propenal of at leastabout 25 mg/kg soil (or at least about 50 mg/kg soil, 100 mg/kg soil,200 mg/kg soil, or 300 mg/kg soil).

The disclosed compositions may be utilized to control one or more pests(e.g. parasitic nematodes, fungi, and weeds). In some embodiments, thedisclosed compositions are applied to soil at a given rate (e.g., about1 ml/kg soil, about 2 ml/kg soil, about 3 ml/kg soil, or about 4 ml/kgsoil) and reduce the pest population in the soil (e.g., parasiticnematodes as measured by number of pests/mls soil) by at least about 50%(or at least about 60%, 70%, 80%, or 90%). In further embodiments, thedisclosed compositions do not significantly reduce the population ofbeneficial nematodes present in the soil (e.g., microbivores), where thedisclosed composition are applied to soil at a given rate (e.g., about 1ml/kg soil, about 2 ml/kg soil, about 3 ml/kg soil, or about 4 ml/kgsoil) and do not reduce the beneficial nematode population in the soilby more than about 50% (or no more than about 40%, 30%, 20%, or 10%).

ILLUSTRATIVE EMBODIMENTS

The following list of embodiments is illustrative and is not intended tolimit the scope of the claimed subject matter.

Embodiment 1

A soil-amendment composition for controlling soil-bourne pests, thecomposition comprising: (a) an effective amount of a treated crudeglycerin composition, wherein the crude glycerin composition is obtainedas a by-product of a reaction mixture for producing biodiesel fuel andthe crude glycerin composition is treated by: (i) adjusting the pH ofthe crude glycerin composition to about 4.0-6.8 to obtain a neutralizedcomposition; and (ii) removing an insoluble precipitate from theneutralized composition; thereby obtaining the treated crude glycerincomposition; and (b) an effective amount of a nitrogen source; whereinthe composition has a molar ratio of total carbon to total nitrogen(C:N) of about (22.4-5.6):1, preferably about (16.8-11.2):1.

Embodiment 2

The soil-amendment composition of embodiment 1, wherein the crudeglycerin composition is further treated by: (iii) heating theneutralized composition; and (iv) removing a volatile distillatefraction from the neutralized composition; thereby obtaining the treatedcrude glycerin composition.

Embodiment 3

The soil-amendment composition of embodiment 2, wherein the crudeglycerin composition is further treated by: (v) refluxing theneutralized composition; and (vi) distilling and collecting a volatiledistillate fraction; thereby obtaining the treated crude glycerincomposition.

Embodiment 4

The composition of any of embodiments 1-3, wherein the soil-bourne pestsare parasitic nematodes.

Embodiment 5

The composition of any of embodiments 1-4, wherein the composition iseffective for reducing parasitic nematodes by at least about 50% whenapplied at an application rate of about 1 ml/kg soil.

Embodiment 6

The composition of any of embodiments 1-5, wherein the composition doesnot reduce microbivorous nematodes by more than about 50% when appliedat an application rate of about 1 ml/kg soil.

Embodiment 7

The composition of any of embodiments 1-6, wherein the reaction mixturefor producing biodiesel fuel comprises: (a) animal or vegetable fats oroils, or a mixture thereof; (b) a base, wherein the reaction mixture hasa pH of at least about 11; and (c) an alcohol.

Embodiment 8

The composition of embodiment 4, wherein the base is selected from thegroup consisting of NaOH, KOH, NaOCH₃ and KOCH₃.

Embodiment 9

The composition of embodiment 4, wherein the alcohol is methanol orethanol.

Embodiment 10

The composition of any of embodiments 1-9, wherein prior to beingtreated the crude glycerin composition comprises: (a) about 65-85%glycerin; (b) acrolein; (c) monoglycerides; and (d) alcohol; and thecrude glycerin composition has a pH of greater than about 11.

Embodiment 11

The composition of any of embodiments 1-10, wherein the treated crudeglycerin composition comprises: (a) about 65-85% glycerin; and (b)acrolein; and (c) no more than about 10% monoglycerides (preferably nomore than about 8%, 6%, 4%, or 2% monoglycerides).

Embodiment 12

The composition of embodiment 2, wherein the treated crude glycerincomposition comprises: (a) about 65-85% glycerin; and (b) acrolein; and(c) no more than about 15% alcohol (preferably no more than 10% or 5%alcohol).

Embodiment 13

The composition of embodiment 3, wherein the treated crude glycerincomposition comprises: (a) about 65-85% glycerin; and (b) at least about5% acrolein (preferably at least about 10% or 15% acrolein).

Embodiment 14

The composition of any of embodiments 1-13, wherein adjusting the pH ofthe crude glycerin composition to about 4.0-6.8 comprises adding an acidto the composition.

Embodiment 15

The composition of embodiment 14, wherein the acid is an organic acid.

Embodiment 16

The composition of embodiment 14, wherein the organic acid is acarboxylic acid.

Embodiment 17

The composition of embodiment 16, wherein the carboxylic acid is aceticacid, propionic acid, butyric acid, or a mixture thereof.

Embodiment 18

The composition of embodiment 14, wherein the organic acid is apolyhydroxy carboxylic acid.

Embodiment 19

The composition of embodiment 18, wherein the polyhydroxy carboxylicacid is citric acid.

Embodiment 20

The composition of embodiment 14, wherein the acid is an inorganic acid.

Embodiment 21

The composition of embodiment 20, wherein the inorganic acid isphosphoric acid or sulfuric acid (preferably phosphoric acid).

Embodiment 22

The composition of embodiment 14, wherein the acid is a mixture of anorganic acid and an inorganic acid.

Embodiment 23

The composition of embodiment 2, wherein heating comprises heating theneutralized composition to a temperature of at least about 80° C.(preferably at least about 80° C. or 90° C.) under vacuum, preferably atleast about 500 mm Hg (19 inch Hg), 600 mm Hg (23 inch Hg), or 700 mm Hg(27 inch Hg).

Embodiment 24

The composition of embodiment 3, wherein refluxing comprises heating theneutralized composition to a temperature of about 200-350° C.(preferably at a temperature of about 200-300° C. or about 220-250° C.)through a condenser; and distilling comprises heating the neutralizedcomposition and collecting distillates through a temperature range ofabout 40-250° C.

Embodiment 25

The composition of any of embodiments 1-24, wherein the nitrogen sourceis an organic nitrogen source (e.g., urea, casein, or a mixturethereof).

Embodiment 26

The composition of any of embodiments 1-25, wherein the crude glycerincomposition further is treated by reacting the composition with sodiumbisulfate or potassium bisulfate.

Embodiment 27

The composition of any of embodiments 1-26, further comprising sulfur.

Embodiment 28

A method for preparing a soil-amendment composition for controllingsoil-bourne pests, the method comprising combining: (a) an effectiveamount of a treated crude glycerin composition, wherein the crudeglycerin composition is obtained as a by-product of a reaction mixturefor producing biodiesel fuel and the crude glycerin composition istreated by: (i) adjusting the pH of the crude glycerin composition toabout 4.0-6.8 to obtain a neutralized composition; and (ii) removing aninsoluble precipitate from the neutralized composition; therebyobtaining the treated crude glycerin composition; and (b) an effectiveamount of an organic nitrogen source; wherein the composition has amolar ratio of total carbon to total nitrogen (C:N) of about(22.4-5.6):1, preferably about (16.8-11.2):1.

Embodiment 29

The method of embodiment 28, wherein the crude glycerin composition isfurther treated by: (iii) heating the neutralized composition; and (iv)removing a volatile distillate fraction from the neutralizedcomposition; thereby obtaining the treated crude glycerin composition.

Embodiment 30

The method of embodiment 29, wherein the crude glycerin composition isfurther treated by: (v) refluxing the neutralized composition; and (vi)distilling and collecting a volatile distillate fraction; therebyobtaining the treated crude glycerin composition.

Embodiment 31

A method for preparing a soil-amendment composition for controllingsoil-bourne pests, the method comprising: (a) adjusting the pH of acrude glycerin composition to about 4.0-6.8 to obtain a neutralizedcomposition; wherein the crude glycerin composition is obtained as aby-product of a reaction mixture for producing biodiesel fuel; (b)removing an insoluble precipitate from the neutralized composition,thereby obtaining a treated crude glycerin composition; and (c)combining an effective amount of the treated crude glycerin compositionand an effective amount of an organic nitrogen source such that thecomposition has a molar ratio of total carbon to total nitrogen (C:N) ofabout (22.4-5.6):1, preferably about (16.8-11.2):1.

Embodiment 32

The method of embodiment 31, further comprising heating the neutralizedcomposition; and removing a volatile distillate fraction from theneutralized composition; thereby obtaining the treated crude glycerincomposition.

Embodiment 33

The method of embodiment 32, further comprising refluxing theneutralized composition; and distilling and collecting a volatiledistillate fraction; thereby obtaining the treated crude glycerincomposition.

Embodiment 34

A method for controlling soil-bourne pests comprising applying a liquidsoil-amendment composition at an application rate of at least about 1ml/kg soil, the soil-amendment composition comprising: (a) an effectiveamount of a treated crude glycerin composition, wherein the crudeglycerin composition is obtained as a by-product of a reaction mixturefor producing biodiesel fuel and the crude glycerin composition istreated by: (i) adjusting the pH of the crude glycerin composition toabout 4.0-6.8 to obtain a neutralized composition; and (ii) removing aninsoluble precipitate from the neutralized composition; therebyobtaining the treated crude glycerin composition; and (b) an effectiveamount of an organic nitrogen source; wherein the composition has amolar ratio of total carbon to total nitrogen (C:N) of about(22.4-5.6):1, preferably about (16.8-11.2):1.

Embodiment 35

The method of embodiment 34, wherein the crude glycerin composition isfurther treated by: (iii) heating the neutralized composition; and (iv)removing a volatile distillate fraction from the neutralizedcomposition; thereby obtaining the treated crude glycerin composition.

Embodiment 36

The method of embodiment 35, wherein the crude glycerin composition isfurther treated by: (v) refluxing the neutralized composition; and (vi)distilling and collecting a volatile distillate fraction; therebyobtaining the treated crude glycerin composition.

EXAMPLES

The following examples are illustrative and are not intended to limitthe scope of the claimed subject matter.

Example 1 Neutralization of Crude Glycerin Product (CGP) from BiodieselProduction

A crude glycerin product (CGP) is produced from a transesterificationreaction between sodium (or potassium) methylate and vegetable or animaloils or fats (i.e., glycerin esters of fatty acids). Thetransesterification reaction produces biodiesel (i.e., methyl esters ofthe fatty acids) and about 12-14% CGP. The pH of CGP is typically in therange of 11.5-12.5 and most commonly 12.00. Use of the CGP inagriculture requires lowering of pH to within an acceptable level foraddition to soil (e.g., a pH of about 5.8-6.5).

Procedure.

CGP was obtained from Alabama Biodiesel Corporation, Moundville, Ala.,producers of biodiesel from food grade soybean oil. In the typicallaboratory procedure, 32 mls of propionic acid are added slowly in 5-8ml aliquots while stirring into filtered and clear 500 mls CGP. A finalpH of 6.5 is attained. During the neutralization process, when the pHnears about 8.00, a clouding is observed due to precipitation of freelong-chained fatty acids. These acids are either present in thevegetable oil or may be formed during the trans-methylation reaction—theacids react with Na⁺ or K⁺ cations to form fatty acid salts (i.e.,soaps). On standing overnight (10-14 hrs) at room temperature (20-23°C.), the soaps float to the surface of the neutralized mixture and areseparated from the clear underlying neutralized bioglycerin (NBG). Theamount of soap collected amounts to some 10-15% of the final volume whenpropionic acid is used.

Other acids that can be used and the amount needed for neutralization(parenthesis) of 500 mls CGP to pH 6.5 are: glacial acetic (17 mls);butyric acid (30 mls); valeric acid (38 mls); citric acid (19 gms); 96%sulfuric acid (7 mls); 85% phosphoric acid (14 mls). The amount of soapformed varies considerably among the acids. The preferred organic acidsare acetic acid and propionic acid. The preferred inorganic acid isphosphoric acid. A 2:1 mixture of (propionic acid):(phosphoric acid) ispreferred when NBG is to be used as an organic amendment tosoil—phosphoric acid providing the necessary phosphorus for microbialmetabolism and plant growth.

NBG thus prepared can be added directly to soil for control of nematodesand other soil-borne pests. (See Example 4 and FIGS. 1-3 and 10-12.) Ittypically contains by volume: glycerin (˜73%), recoverable volatiles(˜23%), and unrecoverable volatiles (4%). The amount of glycerin andvolatiles will vary with the type of oil or fat used to make biodieseland the acid used to neutralize CGP.

Example 2 Removal of Volatile Components from Neutralized Bioglycerin(NBG)

Neutralized bioglycerin (NBG) contains significant amounts of volatilecompounds that preferably are removed prior to thermal reduction ofglycerin (i.e., refluxing) and formation of acrolein (i.e., 2-propenal)and related enal compounds with pesticidal properties. (See pending U.S.application Ser. No. 11/260,771, which content is incorporated herein byreference in its entirety).

Procedure.

500 mls NBG are placed in a 2 L round bottom flask which is connected toa rotary evaporator (Evapotec, Haaken Buehler) and lowered into a waterbath set with water at 90° C. The flask is then rotated at 200 rpm andvacuum is applied at −700 mm Hg (−27 inch Hg) while cool water (5° C.)is run through the condenser coils. Volatiles are collected in a 1 Lround bottom flask attached to bottom of the condenser section of theapparatus. The operation is stopped after approx. 30 min when 95-98% ofvolatiles are collected. The glycerin in the 2 L flask is nowessentially free of low boiling compounds and is ready for refluxing andthermal reduction and distillation. Volatiles collected consist ofmethanol, and residual propionic acid, esters, and turpentine-likesmelling compounds of unknown identity.

Example 3 Refluxing and Distillation of Neutralized Bioglycerin (NBG)

Condensation and reduction of glycerin occurs in nature during theburning of fats and oils. The process results in formation of acrolein(i.e., 2-propenal) and polymers thereof. These enal compounds because oftheir conjugate double bond with aldehyde group are very reactive andhave a strong broad-spectrum of pesticidal activities (weeds, nematodes,fungi . . . etc.). The reduction and condensation of glycerin can becatalyzed by strong acids (especially H₂SO₄ or NaHSO₄). Acid, however,may not be required if the glycerin is heated at temperatures of about200-300° C. In this manner, it is possible to enrich “stripped NBG” ofits acrolein content and increase its pesticidal properties. “StrippedNBG” refers to NBG having reduced volatiles after having performed themethod described in Example 2.

Procedure.

Step 1. 500 mls of stripped NBG is placed in a 2 L round-bottom flask ina Barnstead Magnistir variable heater and heated to about 110° C. forabout 15-20 min while stirring vigorously. This step helps reduce oreliminate any residual water. A Liebig type condenser is then fittedupright into the neck of the 2 L flask, cool water (about 5-10° C.) isrun through the condenser and the temperature is gradually increased toabout 220-250° C.; the liquid thus being refluxed is kept stirredvigorously for about 60-90 min while manipulating the temperature toavoid foaming. At the end of the refluxing period, the temperature isslowly reduced to less than about 40° C. and the condenser is carefullyremoved. A brown to dark liquid with a lachrymatory acrid vapor(producing tears) should be present in the flask.

Step 2. The 2 L flask with reduced glycerin from step 1 and still in theheater, is now connected to a simple column distillation apparatus. Thetemperature is gradually increased and distillates are collected througha temperature [T] range of about 40≦T<250° C. The distilled fraction canbe added directly to soil for control of nematodes and other soil-bornepests. (See Example 4 and FIGS. 4-9).

Comments.

Removal of soaps after neutralization of CGP may be essential to avoidexcessive foaming. The pH of stripped NBG preferably should be on theacid side, preferably in the range of about 4.5-5.5. If necessary thiscan be attained by adjusting the pH with H₃PO₄. The chemical compositionof the various distillates is quite varied and at this point notcompletely elucidated. They all contain some acrolein with most of thatcompound distilling over in the range of about 50-100° C. Higher boilingdistillates are presumed to be polymers of the compound as well as otherchemically reduced unknown entities.

Example 4 Use of Treated Crude Glycerin Products as Soil Amendments

Objective 1.

Factorial greenhouse experiments will be established to determine theefficacy of glycerin containing increasing concentrations of acroleinfor control of the reniform nematode (Rotylenchulus reniformis), and ofcommon damping off and seedling disease fungi (Rhizoctonia solani, andspecies of Pythium and Fusarium). Soils for these experiments will benaturally infested with the pathogens and obtained from fields known tobe infected with nematodes or fungi. In each experiment, the moist soil(60% field capacity) will be apportioned in 1 kg amounts contained in 1L cylindrical PVC pots with 1 mm mesh non-metal screen bottoms.Glycerin-acrolein mixtures will be delivered by drenching in 100 mlsaqueous solutions/pot (equivalent to 1 acre inch water). Immediatelyafter treatment, the pots will be covered with polyethylene bags (2 mil)and placed on a greenhouse bench. The bags will be removed after 2 wksand soil samples will be taken for nematological analyses by the saladbowl incubation technique (Rodriguez-Kabana & Pope, Nematropica11:175-186 (1987)). “Hutchenson” soybean (reniform nematode susceptible)will be planted (5 seed/pot) and allowed to grow for 6 weeks when theplants will be removed and data collected on: number of survivingplants, phytotoxicity, and plant growth parameters (shoot height andweights of shoots and roots), and nematode populations in soil and rootsystems (salad bowl incubation).

In experiments with fungal pathogens, 20 annual morning glory seed(mixture of Ipomoea hederacea and I. lacunosa seed) will be uniformlydistributed and slightly pressed onto the soil surface of each pot. Theseeds will be covered with approx. 5 mm layer of moist fine siliceoussand. The number of emerging morning glory plants will be determinedevery 5-7 days for one month. Previous studies have shown that thenumber of emerging plants is inversely related to the level of dampingoff and seedling disease (unpublished data). Experiments on herbicidalactivity will be performed using a sandy loam soil from a field,characterized as not having a significant nematode or fungal diseaseproblem. The soil will be apportioned in 1 kg amounts and placed in 6 Lpolyethylene bags (“chicken bags”). Soil in each bag will be thoroughlymixed with a weed seed mixture. The mixture consists of 5 yellownutsedge rhizomes and the seed of (number per bag): annual morning glorymix, i.e., Ipomoea hederacea/I. lacunosa, (40); large crabgrass, i.e.,Digitaria sanguinalis, (300); sicklepod, i.e., Senna obtusifolia, (60);jimsonweed, i.e., Datura stramonium, (80); yellow foxtail, i.e., Setariaglauca, (100); and redroot pigweed, i.e., Amaranthus retroflexus,(1000). The soil with weeds will be transferred to pots and treated asdescribed for the experiments with nematodes and fungi. The number andspecies of emerging weeds will be recorded at weekly intervals for 6 wksafter removal of the plastic bags.

There will be 14 treatments in each experiment arranged in a randomizedcomplete block design with 7 replications (experimental unit=1 pot) pertreatment for a total of 98 pots. It is envisioned that there will be aminimum of 6 experiments within this objective.

Objective 2.

The ideal C/N ratios for glycerin acrolein mixtures to assure completedecomposition of the mixtures in soil without phytotoxic effects tosucceeding crop plants will be determined. Glycerin and acrolein containno nitrogen, so their decomposition in soil will be limited by theamount of available N in soil. The treatments may result not only inpartial decomposition of glycerin-acrolein added but also in adeficiency of available N and “yellowing” of crop plants. Greenhouseexperiments will be conducted. to determine the optimal amount of Nneeded to optimize microbial decomposition of glycerin-acrolein mixturesestablished from Objective I while still retaining pesticidal activity.Factorial experiments will be set up with treatments consisting ofmixtures of an organic N source (e.g., urea, casein) andglycerin-acrolein solutions with the highest pesticidal activities asdetermined from Objective 1. The tested nitrogen sources will includeurea and casein, which are both relatively inexpensive, commerciallyavailable, and exhibit considerable solubility in glycerin (Merck Index,1989). The experiments will be set up as described for Objective 1 todetermine pesticidal activities (including nematocidal, fungicidal, andherbicidal activities) of the glycerin acrolein-urea (GAU) and theglycerin-urea-casein (GUC) compositions.

Objective 3.

Develop formulations suitable for field use and determine theirperformance for nematode control and yield response in microplotexperiments with tomato and other common horticultural crops. Liquidformulations of GAU and GUC suitable for application through irrigationwater will be developed based on results obtained from Objective 2. Theformulations will be tested in microplot experiments at the MicroplotExperimental Unit on the Auburn University campus. A microplot consistsof an 1 ft² area delimited by a 2 ft-long square terra cotta chimneyflue embedded in soil with 4 inches set above ground. The microplots arefilled with silt-loam soil known to be infested with a variety of plantpathogenic nematodes (including Meloidogyne incognita, Hoplolaimusgaleatus, Paratrichodorus minor, and others), and fungi (including, R.solani and species of Pythium and Fusarium). Microplots are fitted witha drip irrigation system in which each plot has a dripper delivering 2gallons of water per hour.

Microplots will be treated by drenching in 1 inch-acre of water with theappropriate glycerin formulations. Immediately after application of thetreatments, the plots will be covered with clear polyethylene (2 mil)mulch. After 3 wks, the mulch will be removed and soil samples fornematological analyses will be collected. Each plot will then be plantedwith seedlings (2/plot). There will be a minimum of 3 experiments, onewith cherry tomatoes and the other two with eggplant and green pepper.The plants will be irrigated and maintained in good growing conditionsfollowing standard recommendations for production of the crops. Eachmicroplot experiment will have 8 treatments with 8 replications arrangedin a randomized complete block design. There will be thus 64 plots perexperiment and crop.

Data will be collected on plant survival, phytotoxicity, growthparameters and yield. Soil and root samples will be collected attermination of the experiments to determine nematode populations and toestimate damage from fungal pathogens. Yield data will be used inpreliminary economic analyses.

Example 5 Treated Crude Glycerin Combined with Organic Nitrogen

The effect of neutralized bioglycerin (NBG), either in the presence orabsence of organic nitrogen, was tested on the growth of cotton plantsand parasitic nematodes. Neutralized bioglycerin (NBG) was applied atrates of 0, 1, 2, 3, 4, and 5 mls/kg soil either with or without urea(150 mgs/Kg soil of the compound to achieve about 70 mgs N/Kg soil).Applications were performed by drenching the soil in aqueous solution sothat the final application volume per pot was 100 mls (which isequivalent to an acre inch of irrigation). Each pot contained 1 Kg ofsoil infested with the reniform nematode Rotylenchulus reniformis andthere were 7 replications (pots)/treatment. Thus, for example, for the 1ml NBG application there were 14 pots, 7 of which received each water upto 100 mls containing 1 ml NBG; the other 7 pots received each 1 mlNBG+150 mgs urea mixed in a final volume of 100 mls. The carbon:nitrogenratios (C/N) of the combined treatments ranged from about 5.6 for the 1ml NBG treatment to 28 for the 5 mls NBG treatment. Urea alone (0 mlsNBG) suppressed reniform nematode numbers but proved phytotoxic tocotton plants where a lower number of cotton plants per pot wereobserved. Applications of NBG without urea, while detrimental to thenematode (see FIG. 10), did not improve cotton plant survival and infact was somewhat detrimental to the plants (see FIGS. 11 & 12). FIGS.11 & 12 suggest that C:N ratios in the range of about 5.6≦C/N≦22.4(i.e., 1≦NBG≦4 mls/Kg soil) are optimal for nematode control andsurvival of cotton plants (preferably in the range of about11.2≦C/N≦16.8 (i.e., 2≦NBG≦3 mls/Kg soil)).

Urea is soluble in NBG up to 40% by weight so that the two materials canbe formulated together. Ideally, the pH should be adjusted between about4.0 and about 5.5. Buffers composed of K salts of H₃PO₄ and propionicacid (or other organic acids) may be particularly suitable because theyform strong buffers for the required pH range and contain the nutrientsP and K. Other N compounds that can be utilized in lieu of urea include,but are not limited to, guanidines, dicyandiamide, and oxamide. Afteradding water to the NBG (e.g., about 10-20%) standard nitrates (K or NH₄⁺) or even ammonium sulfate and the like can be utilized for preparingfertilizer mixtures having pesticidal properties. Alternatively, thenitrate or ammonium salts may be added to the NBG as aqueous solutions.

Example 6 Use of Untreated Crude Biodiesel Glycerin for Controlling orEliminating Weeds

The efficacy of untreated crude biodiesel glycerin for controlling oreliminating weeds was tested against crab grass, sickle pod, and morningglory. The untreated bioglycerin was applied to soil at rates of 5mls/kg soil, 10 mls/kg soil, 11 mls/kg soil, 12 mls/kg soil, 13 mls/kgsoil, 14 mls/kg soil, 15 mls/kg soil, 16 mls/kg soil, 17 mls/kg soil, 18mls/kg soil, 19 mls/kg soil, and 20 mls/kg soil. After 5, 11, 19, or 39days, the soil was mixed with weed seed and emerging seeds wereperiodically counted. Application rates of untreated bioglycerin as lowas 10 mls/kg soil were found to be effective for reducing emergingweeds. Thus, untreated crude biodiesel glycerin may be utilized as suchas a soil-amendment for controlling or eliminating weeds, or optionally,further may be treated as disclosed herein (e.g., neutralized, heated,refluxed, condensed, distilled, and combined with additional pesticidalor fertilizing agents).

All publications and patent applications cited in this specification areherein incorporated by reference as if each individual publication orpatent application were specifically and individually indicated to beincorporated by reference.

1.-25. (canceled)
 26. A soil-amendment composition for controllingsoil-borne pests, the composition comprising: (a) an effective amount ofa treated crude glycerin composition, wherein the treated crude glycerincomposition is treated by adding an organic acid to a crude glycerincomposition; and (b) an effective amount of a glycerin-soluble nitrogensource.
 27. The composition of claim 26, wherein the organic acid is acarboxylic acid.
 28. The composition of claim 26, wherein the carboxylicacid is selected from a group consisting of acetic acid, propionic acid,butyric acid, valeric acid, citric acid or a mixture thereof.
 29. Thecomposition of claim 26, wherein the crude glycerin compositioncomprises glycerin obtained as a by-product of a reaction mixture forproducing biodiesel fuel.
 30. The composition of claim 29, wherein thereaction mixture for producing biodiesel fuel comprises: (a) animal fat,vegetable oil, or a mixture thereof; (b) a base, wherein the reactionmixture has a pH of at least about 11; and (c) an alcohol selected froma group consisting of methanol, ethanol, and a mixture thereof.
 31. Thecomposition of claim 30, wherein the base is selected from the groupconsisting of NaOH, KOH, NaOCH₃ and KOCH₃.
 32. The composition of claim26, wherein the treated crude glycerin composition has a pH of about4.0-8.0.
 33. The composition of claim 26, wherein the treated crudeglycerin composition has a pH of about 4.0-6.8.
 34. The composition ofclaim 26, wherein the nitrogen source comprises urea.
 35. Thecomposition of claim 26, further comprising assimilable phosphorus. 36.The composition of claim 26, wherein the treated crude glycerincomposition is further treated by adding a phosphorus-containing acid.37. The composition of claim 35, wherein the phosphorus-containing acidis phosphoric acid.
 38. The composition of claim 35, wherein thephosphorus-containing acid is phosphorous acid.
 39. The composition ofclaim 26, further comprising assimilable potassium.
 40. The compositionof claim 26, further comprising sulfur.
 41. The composition of claim 26,wherein the treated crude glycerin composition is further treated byadding sulfuric acid.
 42. The composition of claim 26, wherein thetreated crude glycerin composition is further treated by reacting thecomposition with sodium bisulfate or potassium bisulfate.
 43. Thecomposition of claim 26, further comprising a pesticide.
 44. Thecomposition of claim 26, wherein prior to being treated the crudeglycerin composition comprises: (a) about 65-85% glycerin; (b) acrolein;(c) no more than about 5% monoglycerides; and (d) no more than about 5%alcohol; and the crude glycerin composition has a pH of greater thanabout
 11. 45. A method for preparing a soft-amendment composition forcontrolling soil-borne pests, the method comprising combining: (a) aneffective amount of a treated crude glycerin composition, wherein thetreated crude glycerin composition is treated by adding a organic acidto a crude glycerin composition; and (b) an effective amount of aglycerin-soluble nitrogen source.
 46. The method of claim 45, whereinthe organic acid is a carboxylic acid.
 47. The method of claim 46,wherein the carboxylic acid is selected from a group consisting ofacetic acid, propionic acid, butyric acid, valeric acid, citric acid ora mixture thereof.
 48. The method of claim 45, wherein the crudeglycerin composition has a pH that is basic and the organic acid isadded in an amount effective for adjusting the pH of the crude glycerincomposition to but 4.0-8.0.
 49. The method of claim 45, wherein thecrude glycerin composition has a pH that is basic and the organic acidis added in an amount effective for adjusting the pH of the crudeglycerin composition to about 4.0-6.8.
 50. The method of claim 45,wherein the treated crude glycerin composition is further treated byremoving an insoluble precipitate after the organic acid is added to thecrude glycerin composition.
 51. The method of claim 45, wherein thenitrogen source comprises urea.
 52. The method of claim 45, wherein thetreated crude glycerin composition is further treated by: (iii) heatingthe crude glycerin composition; and (iv) removing a volatile distillatefraction; thereby obtaining the treated crude glycerin composition. 53.The method of claim 45, wherein the treated crude glycerin compositionis further treated by: (v) refluxing the crude glycerin composition; and(vi) distilling and collecting a volatile distillate fraction; therebyobtaining the treated crude glycerin composition.
 54. A method forcontrolling soil-borne pests comprising applying the soil amendmentcomposition of claim 26 to soil.
 55. The method of claim 54, comprisingapplying the composition at an application rate of about 1 ml/kg soil.56. A method for controlling soil-borne pests, the method comprising:(a) preparing a soil-amendment composition having an effective amount ofa treated crude glycerin composition, wherein the treated crude glycerincomposition is treated by adding an organic acid to a crude glycerincomposition to obtain a generally neutralized composition; (b) applyingthe soil-amendment composition to soil wherein the soil includes anitrogen source.
 57. The method of claim 56 wherein the organic acid isa carboxylic acid.
 58. The method of claim 56, wherein the treated crudeglycerin composition has a pH and the organic acid is added in an amounteffective for adjusting the pH of the generally neutralized compositionto about 4.0-8.0.
 59. The method of claim 56, wherein the soil-amendmentcomposition further comprises an effective amount of a glycerin-solublenitrogen source.
 60. The method of claim 56, wherein the nitrogen sourceis added to the soil prior to applying the soil-amendment composition.61. (canceled)
 62. The method of claim 56, further comprising adding aninorganic acid to the crude glycerin composition in conjunction with theorganic acid to obtain the generally neutralized composition.